US5855863A - Zeolite L preparation - Google Patents

Zeolite L preparation Download PDF

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US5855863A
US5855863A US08/461,797 US46179795A US5855863A US 5855863 A US5855863 A US 5855863A US 46179795 A US46179795 A US 46179795A US 5855863 A US5855863 A US 5855863A
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zeolite
particles
catalyst
alkali metal
binderless
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Johannes Petrus Verduijn
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/222—Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/28—LTL, e.g. BA-G, L, AG-1, AG-2, AG-4, BA-6

Definitions

  • This invention relates to the preparation of substantially binderless particles of zeolite L, particularly in the form of aggregates for use in catalysis, particularly for aromatisation.
  • Zeolite L has been known for some time as an adsorbant, and in U.S. Pat. No. 3,216,789 is described as an aluminosilicate of the formula:
  • zeolite L (where M is an exchangeable cation of valency n and y is from 0 to 9) having a characteristic X-ray diffraction pattern.
  • the preparation of zeolite L is described in U.S. Pat. No. 3,216,789, EP-A-167755, EP-A-142355, EP-A-142347, EP-A-142349, EP-A-109199, PL-A-72149, U.S. Pat. No. 3,867,512, and SU-548567.
  • EP-A-96479 describes and claims zeolite L having a characteristic morphology and size, which is particularly valuable for use as a catalyst base in hydrocarbon conversions such as aromatisation, and comprising crystallites in the form of cylinders with a mean diameter of at least 0.1 micron, preferably at least 0.5 micron.
  • EP-A-96479 describes a synthesis of zeolite L which is conducted so that the amount of the contaminant zeolite W, which is know to grow in such a system as a competitive phase, is minimised.
  • a preferred synthesis gel described in EP-A-96479 has the following mole ratios:
  • this gel may be varied by changing the molar amount of one component within the following ranges:
  • EP-A-142353, EP-A-142354 and EP-A-185519 describe developments of this process for forming cylindrical zeolite L.
  • Zeolite L may be used as a catalyst base in aromatisation reactions.
  • U.S. Pat. No. 4,104,320 discloses dehydrocyclisation of aliphatic compounds in the presence of hydrogen using a catalyst comprising zeolite L and a group VIII metal.
  • the particular zeolite disclosed in EP-A-96479 is remarkably effective in such aromatisation reactions being capable of forming catalysts which have extended lifetime.
  • Such dehydro- cyclisation and/or aromatisation reactions and catalysts for use in such reactions are also described in EP-A-107389, EP-A-184451, EP-A-142351, EP-A-145289, EP-A-184450, U.S. Pat. No.
  • the product recovered from the usual methods used to prepare zeolite L is a fine sized crystalline material.
  • Several of the uses as catalysts or molecular sieves require a product in a size range substantially larger than the size of the product recovered from the preparation processes of the prior art.
  • various binders are used in forming steps to prepare aggregates containing zeolite L as the principal ingredient such as pellets, extrudates, or tablets. These aggregates lose some of their activity per unit weight since the binder has a different and low activity and acts-as a diluent of the molecular sieve activity and the conventionally-bound aggregates frequently do not have sufficient crushing strength, particularly when they contain the cylindrical zeolite L crystallites as described in EP-A-96479.
  • particles made using alumina as binder are susceptible to blocking of the zeolite pores, as a result of alumina migration. It is therefore highly desirable to develop a method of preparing binderless aggregates having a particle size suitable for catalyst or sieve systems and possessing good attrition resistance.
  • U.S. Pat. No. 3,650,687 describes processes for the preparation of binderless zeolite particles including zeolite L, in which an alumina silicate clay is slurried with an alkali silicate, spray dried to form particles of the desired finished size and then treated with an alkali and aged to convert the particles to zeolite.
  • a hydrated clay is slurried and spray dried to form particles., then calcined and reacted with the other components necessary to form a zeolite.
  • zeolite is only formed after the final particles have been formed. Predictable formation of zeolite having optimum catalytic properties may be difficult under such circumstances.
  • spray drying can be used only to give small particles, typically of 100 to 400 microns, which are only suitable for fluidised beds whereas reactors usually need particle sizes of at least 0.8 mm, preferably at least 1.5 mm and typically 3 mm.
  • GB-A-1316311 describes binderless zeolite particles which may be of zeolite L, and which are formed by pelleting, crush and repelleting repeatedly to give products of the desired strength. This is a time-consuming procedure which is costly and can damage the zeolite crystals.
  • GB-A-2109359 describes the preparation of zeolite 3A and 4A binderless particles in various processes in which kaolin clay and sodium hydroxide (in some cases with zeolite) are formed into beads and then reacted with further sodium hydroxide to form zeolite 4A (sodium form) which is exchanged to form zeolite 3A (potassium form). It is clearly stated that direct formation of a potassium zeolite is not possible in this process.
  • GB-A-2160517 describes the formation of so called preformed zeolite particles, which may be zeolite L particles prepared from a starting material, which may be a synthetic zeolite but must have a silica/alumina ratio lower than the product.
  • the starting material is reacted with a silica material and an alkali to form the product.
  • To form zeolite L either zeolite 3A, kaolin or a silica-alumina starting material is used.
  • the products are necessarily more silica rich than the starting zeolite. This process has practical handling problems in treating particles with a silica containing material.
  • EP-A-284206 (counterpart to U.S. Pat. No. 5,486,348) describes the preparation of binderless zeolite L particles involving the reaction of an alkaline solution comprising a source of alumina with particles formed from silica and 0 to 95 wt % of preformed zeolite L crystallites to convert the silica binder to zeolite L and obtaining the desired particles by crystallisation of the reaction mixture.
  • the present invention concerns a method of preparing binderless zeolite L particles with further enhanced catalytic performance and/or capacity over those prepared by the process of EP-A-284206 and with very high mechanical strength, for example against attrition.
  • the invention also provides certain novel binderless zeolite L particles.
  • binderless particles of zeolite L of very high mechanical strength are prepared by a process comprising reacting substantially binderless particles of zeolite L with an aqueous alkaline solution containing sources of alkali metal and aluminium to obtain the desired particles of very high mechanical strength, wherein at least 50 mole % of the alkali metal is potassium.
  • the FIGURE shows scanning electron micrographs of the interior of the starting and product extrudates prepared in Example 1.
  • binderless zeolite L particles or "binder-free zeolite L particles” refer to a plurality of individual zeolite L crystallites held together without the use of a significant amount of non-zeolitic binder.
  • the particles Preferably contain less than 10 wt % (based on the weight of the total particles) of non-zeolitic binder. More preferably, the particles contain less than 5 wt % of non-zeolitic binders, and it is most preferable for the particles to be substantially free of non-zeolitic binder.
  • any particles e.g. powders or crushed shaped particles, may be used as starting material, preferably they are shaped particles, e.g. as tablets or pellets and they are usually formed by extrusion.
  • the binderless particles or binderless shaped particles of zeolite L used as the starting material for the process of this invention are preferably obtained by the process of EP-A-284206.
  • the zeolite L crystallites are used as starting material which in turn may be prepared by any of the known procedures.
  • the zeolite L comprises crystallites in the form of cylinders with a mean diameter of at least 0.05 micron, preferably at least 0.1 micron, typically at least 0.5 micron (such as described in EP-A-96479), and most preferably the crystallites have the basal planes shaped such that the ratio of axial length of curved cylindrical surface (1) to the overall axial length of the crystallite (h) is greater than 0.9, optimally substantially unity.
  • XRD--substantially invisible material prepared by the process of patent application Ser. No. 292,704, now U.S. Pat. No. 5,064,630.
  • the zeolite L used as starting material, and in the final particle of the process of EP-A-284206, is preferably an aluminosilicate and although described as an aluminosilicate, other elemental substitutions are possible; for example aluminium may be substituted by gallium, boron, iron and similar trivalent elements, and silicon may be substituted by elements such as germanium or phosphorus.
  • the aluminosilicates preferably have a composition (expressed in terms of molar ratios of the constituent oxides in anhydrous form) of:
  • M is a cation of valence n, x is from 4 to 7.5.
  • the exchangeable cation M comprises potassium, although it is possible for a part of the potassium to be replaced by other cations such as alkali and alkaline earth metals for example sodium, rubidium or caesium.
  • the zeolite L may also contain, preferably at non-exchangeable sites, copper, magnesium, calcium, barium, lead, iron, manganese, chromium, cobalt, nickel or zinc.
  • the starting material i.e. binderless particles of zeolite, preferably in the form of shaped particles, such as extrudates, are obtained by the process described in EP-A-284206, any binderless zeolite L starting materials may be used.
  • the binderless particles of zeolite L are mixed with an aqueous alkaline solution containing sources of alkali metal and aluminium. It is preferred that the alkali metal is entirely potassium or potassium together with other metals such as caesium, lithium or rubidium. In the case where other metals are present there must be at least 50 mole % of potassium present. Particularly suitable is a mixture of potassium and caesium ions.
  • the source of alkali metal in the reaction mixture is preferably obtained by using the alkali metal hydroxide, but one can use other salts such as the chloride, fluoride or nitrate, provided that the solution is alkaline.
  • the molar ratio expressed as oxide K 2 O/(M 2 O+K 2 O), M being alkali metal other than K, is preferably between 0.7 and 1.0.
  • the alkalinity of the reaction mixture expressed as K 2 O/H 2 O molar ratio is from 0.007 to 0.028, and more preferably between 0.011 and 0.022.
  • the source of aluminium is preferably obtained by using alumina or aluminium hydroxide. If the source of alkali metal is obtained by the use of alkali metal oxide, hydroxide or carbonate then aluminates can be formed by using aluminium metal.
  • the concentration of aluminium in the aqueous solution is such that expressed as Al 2 O 3 the molar ratio of Al 2 O 3 to water is at least 0.0015 and preferably between 0.002 and 0.006.
  • the binderless particles or shaped particles of zeolite L are mixed with the aqueous solution containing alkali metal and aluminium such that the binderless particles are at least wetted by the aqueous solution.
  • this mixture is heated in an autoclave to bring about re-crystallisation.
  • This treatment is generally carried out in a sealed autoclave and thus at autogenous pressure. It is generally inconvenient, although possible to employ higher pressures. Lower pressure (and lower temperature) will require longer re-crystallisation times.
  • Crystallisation time is related to the crystallisation temperature.
  • the re-crystallisation is preferably carried out at from 100° C. to 200° C. and at this temperature the crystallisation time is typically from 12 hours, e.g. 15 to 96 hours.
  • the zeolite may be separated, washed and dried in the normal manner.
  • the product of the invention shows aluminium enrichment compared with the starting material and scanning electron micrographs of the product of this invention show the presence of newly formed submicron crystals. It appears that the aluminium enrichment and/or the presence of these submicron crystals within the extrudates increases the mechanical strength.
  • the final product is also particulate.
  • this particulate product can be turned into shaped particles by the use of conventional binder techniques or by the binderless process disclosed in EP-A-284206.
  • the binderless zeolite L particles prepared by the invention are excellent catalyst bases and may be used in conjunction with one or more catalytically-active metals in a wide variety of catalytic reactions.
  • the particular morphology of the crystals appears to result in a particular stable base for catalytically active metals with a surprising resistance to metal catalyst deactivation.
  • the product has shown an increased SiO 2 /Al 2 O 3 ratio which is believed to contribute to the enhanced performance.
  • the particles have increased toluene adsorption capacity as compared to conventionally bound zeolite L, together with increased particle strength.
  • they have displayed low acidity which makes them especially suited to catalytic applications where a low acid site strength is advantageous such as aromatisation.
  • the catalytically-active metal(s) may be, for example, a Group VIII metal such as platinum, or tin or germanium as described in U.S. Pat. No. 4,104,320, or a combination of platinum and rhenium as described in GB-A-2004764 or BE-A-888365.
  • the catalyst may for appropriate circumstances also incorporate halogen as described in U.S. Pat. No. 4,165,276, silver as described in U.S. Pat. No. 4,295,959 and U.S. Pat. No. 4,206,040, cadmium as described in U.S. Pat. No. 4,295,960 and U.S. Pat. No. 4,231,897 or sulphur as described in GB-A-1600927.
  • catalyst composition to incorporate from 0.1 to 6.0 wt. %, preferably from 0.1 to 1.5 wt. % platinum or palladium, since this gives excellent results in aromatisation. From 0.4 to 1.2 wt. % platinum is particularly preferred, especially in conjunction with the potassium form of the aluminosilicates.
  • the invention extends to catalysts comprising the zeolitic material and a catalytically-active metal.
  • the products of the invention may be used in a process for the conversion of a hydrocarbon feed in which the feed is contacted with a catalyst as described above under appropriate conditions to bring about the desired conversion. They may, for example, be useful in reactions involving aromatisation and/or dehydrogenation reaction.
  • a catalyst comprising binderless zeolite L particle of the invention, preferably having at least 90% of the exchangeable cations as alkali metal ions, and incorporating at least one Group VIII metal having dehydrogenating activity, so as to convert at least part of the aliphatic hydrocarbons into aromatic hydrocarbons.
  • the aliphatic hydrocarbons may be straight or branched chain acyclic hydrocarbons, and particularly paraffins such as hexane, although mixtures of hydrocarbons may also be used such as paraffin fractions containing a range of alkanes possibly with minor amounts of other hydrocarbons. Cycloaliphatic hydrocarbon such as methylcyclopentane may also be used.
  • the feed to a process for preparing aromatic hydrocarbons and particularly benzene comprises hexanes.
  • the temperature of the catalytic reaction may be from 370° to 600° C., preferably 430° to 550° C. and preferably pressures in excess of atmospheric are used, for example up to 2000 KPa, more preferably 500 to 1000 KPa.
  • Hydrogen is employed in the formation of aromatic hydrocarbons preferably with a hydrogen to feed ratio of less than 10.
  • the use of zeolite L with cylindrical morphology enables greatly improved catalyst lifetimes to be achieved as compared to the lifetime obtained with a zeolite L, prepared according to the procedures described in the art prior to EP-A-96479.
  • the invention enables microscopic particles to be prepared from such cylindrical zeolite L, without the use of binder to dilute the performance of the cylindrical crystallites.
  • the aluminium hydroxide was dissolved by boiling and after cooling the aluminate solution was poured into a 150 ml stainless steel autoclave together with the additional water. Next, 20.02 grams of binderfree zeolite L extrudates were added to the contents of the autoclave.
  • reaction mixture was subjected to treatment for 69.5 hrs at 150° C.
  • the product-extrudates were washed with 9 portions of water until a pH of 9.5 was obtained. The total washing time was 25 hours.
  • the product-extrudates were dried at 150° C. for 20 hrs.
  • the weight of the recovered extrudates as 22.70 grams.
  • X-Ray diffraction XRD showed that the product consisted of zeolite L.
  • the apparent XRD-crystallinity versus the starting binderfree extrudates was 82%. This loss in XRD-crystallinity may be due to the presence of the newly formed submicron crystals. It was observed that there was a considerable shift in the d-values compared with those of conventionally prepared zeolite L and this is believed to be due to the aluminium enrichment. Comparative X-Ray data of this product and of conventional zeolite L are given in the Table.
  • Example 1 was repeated using the same amounts of reactants and crystallisation conditions, the only exception was that in this experiment no aluminium hydroxide was used. Upon opening of the autoclave it appeared that the extrudates were completely fallen apart into powder. The product was carefully recovered to avoid any losses during washing. After drying 18.10 grams were recovered, which is 9.5 wt % less than the amount of extrudates used (20.00 grams).
  • Example 1 The procedure of Example 1 was followed and the compositions of the various potassium aluminate solutions (expressed as moles of oxides) ranged from
  • extrudates of zeolite L used as the starting material were binder-free zeolite L obtained according to the process of GB-A-8704365. They had a SiO 2 /Al 2 O 3 mole ratio of approx. 5.1. In all cases 30 grams of extrudate were treated with approximately 59 grams of aqueous potassium aluminate solution.
  • the crush strength was measured as follows:
  • Example 1 The procedure of Example 1 was followed but in two runs with varying amounts of KOH and CsOH. When no potassium is present pollucite is formed instead of zeolite L, and as shown when both potassium and caesium are present zeolite L is formed by with some loss of crystallinity but with no significant contamination. The loss of crystallinity is believed to be due to the presence of caesium.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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US08/461,797 1988-01-19 1995-06-05 Zeolite L preparation Expired - Lifetime US5855863A (en)

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GB888801067A GB8801067D0 (en) 1988-01-19 1988-01-19 Zeolite l preparation
GB8801067 1988-01-19
US29745689A 1989-01-13 1989-01-13
US51795990A 1990-04-30 1990-04-30
US60028190A 1990-10-17 1990-10-17
US16897093A 1993-12-16 1993-12-16
US08/461,797 US5855863A (en) 1988-01-19 1995-06-05 Zeolite L preparation

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EP (1) EP0325465B1 (de)
JP (1) JP2709120B2 (de)
AT (1) ATE74799T1 (de)
CA (1) CA1332398C (de)
DE (1) DE68901182D1 (de)
ES (1) ES2031348T3 (de)
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US6653518B2 (en) 2001-06-15 2003-11-25 Exxonmobil Chemical Patents Inc Reforming process for manufacture of para-xylene
US20180056235A1 (en) * 2016-09-01 2018-03-01 Yu Wang Swing Adsorption Processes Using Zeolite Structures
US10137428B2 (en) 2014-04-09 2018-11-27 W. R. Grace & Co.-Conn Zeolite particles for adsorption and/or desorption of gases and liquids

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JPWO2004003913A1 (ja) 2002-06-28 2005-11-04 富士通株式会社 情報記憶装置
JP4470039B2 (ja) * 2004-05-12 2010-06-02 東ソー株式会社 新規構造ゼオライトおよびその合成方法
KR100769683B1 (ko) * 2006-05-26 2007-10-23 한국해양연구원 인홀형 탄성파콘의 관입시험 방법
FR3123811A1 (fr) * 2021-06-11 2022-12-16 IFP Energies Nouvelles Procede de preparation d'un materiau composite a haute teneur en zeolithe kl et ayant une bonne resistance mecanique
FR3125727A1 (fr) * 2021-07-29 2023-02-03 IFP Energies Nouvelles Procede de preparation d'un materiau zeolithique a haute teneur en zeolithe kl et de haute resistance mecanique

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US6653518B2 (en) 2001-06-15 2003-11-25 Exxonmobil Chemical Patents Inc Reforming process for manufacture of para-xylene
US10137428B2 (en) 2014-04-09 2018-11-27 W. R. Grace & Co.-Conn Zeolite particles for adsorption and/or desorption of gases and liquids
US20180056235A1 (en) * 2016-09-01 2018-03-01 Yu Wang Swing Adsorption Processes Using Zeolite Structures
US10603626B2 (en) * 2016-09-01 2020-03-31 Exxonmobil Upstream Research Company Swing adsorption processes using zeolite structures
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EP0325465A2 (de) 1989-07-26
CA1332398C (en) 1994-10-11
GB8801067D0 (en) 1988-02-17
DE68901182D1 (de) 1992-05-21
ES2031348T3 (es) 1992-12-01
EP0325465B1 (de) 1992-04-15
JPH026324A (ja) 1990-01-10
JP2709120B2 (ja) 1998-02-04
EP0325465A3 (en) 1989-11-02
ATE74799T1 (de) 1992-05-15

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